Process for breaking petroleum emulsions



United States atent PROCESS FOR BREAKING PETROLEUM EMULSIONS Melvin DeGroote, University City, Mo., assignor to Petrolite Corporation,Wilmington, Del., a corporation of Delaware No Drawing. ApplicationNovember 17, 1952, Serial No. 321,037

32 Claims. (Cl. 252-341) This invention relates to a process forbreaking petroleum emulsions of the water-in-oil type and ischaracterized by subjecting such an emulsion to the action of ademulsifier, including certain acidic fractional esters which aredisclosed in my co-pending application S. N. 321,032, filed November 17,1952, and which are derived by esterifying an oxyalkylatedamine-modified phenol-aldehyde resin condensate with a polycarboxy acid.

Ignoring the preparation of the phenol-aldehyde resin per se theremainder of the reactions fall into three classes: (1) Condensation,(2) oxyalkylation, and (3) esterification.

The acidic fractional esters, obtained in the manner herein describedhave utility for various purposes and particularly for the resolution ofpetroleum emulsions of the water-in-oil type. In this connection itshould be noted that the polyhydroxylated reactant or reaction mixturemay be obtained by combining a comparatively large proportion of thealkylene oxide, particularly propylene oxide, or a combination ofpropylene oxide and ethylene oxide, with a comparatively smallproportion of the resin condensate. In some instances the ratio has beenas high as fifty-to-one, i. e., the ultimate product of oxyalkylationcontained about 2% of resin condensate and approximately 98% alkyleneoxide. This was, of course, prior to the esterification step.

Momentarily ignoring the final step or esterification this invention ina more limited aspect, as far as the reactants are concerned which, inturn, are subjected to oxyalkylation and then esterification, are, aspreviously noted, certain amine-modified thermoplastic phenol-aldehyderesins. Subsequent description in regard to the amine-modified resinsemployed is largely identical with the text as it appears in certainco-pending applications, to wit, Serial No. 288,743, filed May 19, 1952,and Serial No. 301,804, filed July 30, 1952. For purpose of simplicitythe invention, purely from a standpoint of the resin condensateinvolved, may be exemplified by an idealized formula as follows:

in which R represents an aliphatic hydrocarbon substituent generallyhaving 4 and not over 18 carbon atoms but most preferably not over 14carbon atoms, and n generally is a small whole number varying from 1 to4. In the resin structure it is shown as being derived from formaldehydealthough obviously other aldehydes are equally satisfactory. The amineresidue in the above structure is derived from a basic amine, andusually a strongly basic amine, and may be indicated thus:

RI HN in which R represents any appropriate hydrocarbon radical such asan alkyl, alicyclic, arylalkyl radical, etc., with the proviso that atleast one of the radicals designated by R has at least one hydroxylradical. The hydrocarbon radical may have the carbon atom chain orequivalent interrupted by oxygen atoms. The only limitation is that theradical should not have a negative radical which considerably reducesthe basicity of the amine, such as an aryl radical or an acyl radical.The introduction of two such amino radicals into a comparativelysmallresin molecule, for instance, one having 3 to 6 phenolic nuclei asspecified, alters the resultant product in a number of Ways. In thefirst place, a basic nitrogen atom, of course, adds a hydrophile effect;in the second place, depending on the size of the radical R, there maybe a counterbalancing hydrophobe eflect or one in which the hydrophobeeffect more than counterbalances the hydrophile effect of the nitrogenatom. The presence of one or more hydroxyl radicals introduces asignificant hydrophile effect. Finally, in such cases where R containsone or more oxygen atoms in the form of an ether linkage another eifectis introduced, particularly another hydrophile effect.

Referring again to the resins as such, it is worth noting thatcombinations, either resinous or otherwise, have been prepared fromphenols, aldehydes, and reactive amines particularly monoamines.

Combinations, resinous or otherwise, have been prepared from phenols,aldehydes, and reactive amines, particularly amines having secondaryamino groups. Generally speaking, such materials have fallen into threeclasses; the first represents non-resinous combinations derived fromphenols as such; the second class represents resins which are usuallyinsoluble and used for the purpose for which ordinary resins,particularly thermo-setting resins are adapted. The third classrepresents resins which are soluble as initially prepared but are notheatstable, i. e., they are heat-convertible, which means they are notparticularly suited as raw materials for subsequent chemical reactionwhich requires temperatures above the boiling point of Water orthereabouts.

As to the preparation of the first class, i. e., non-resinous materialsobtained from phenols, aldehydes and amines, particularly secondaryamines, see United States Patents Nos. 2,218,739 dated October 22, 1940,.to Bruson; 2,033,092 dated March 3, 1936, to Bruson; and 2,036,916dated April 7, 1936,-to Bruson.

As to a procedure by which a resin is produced as such involving allthree reactants and generally result ing in an insoluble resin, or inany event, a resin which becomes insoluble in presence of'addedformaldehyde or the like, see United States Patents Nos. 2,341,907,

dated February 15, 1944, to Che'etham et 211.; 2,122,433, dated July 5,1938, to Meigs; 2,168,335, dated August phatic radical in the ortho orpara position, i. e., the phenols themselves are difunctional phenols.This is a difierentiation from the resins described in theaforementioned Bruson patent, No. 2,031,557, insofar that said patentdiscloses suitable resins obtained from metasubstituted phenols,hydroxybenzene, resorcinol, p,p'(dihydroxydiphenyl)dimethylmethane, andthe like, all of which have at least three points of reaction perphenolic nuclei and as a result can yield resins which may be at leastincipiently cross-linked even though they are apparently still solublein oxygenated organic solvents or else are heat-reactive insofar thatthey may approach insolubility or become insoluble due to the effect ofheat, or added formaldehyde, or both.

' The resins herein employed contain only two terminal groups which arereactive to formaldehyde, i. e., they are difunctional from thestandpoint of methylol-forming reactions. As is well known, although onemay start with difunctional phenols, and depending on the procedureemployed, one may obtain cross-linking which indicates that one or moreof the phenolic nuclei have been converted from a difunctional radicalto a trifunctional radical, or in terms of the resin, the molecule as awhole has a methylol-forming reactivity greater than 2. Such shift cantake place after the resin has been formed or during resin formation.Briefly, an example is simply where an alkyl radical, such as methyl,ethyl, propyl, butyl, or the like, shifts from an ortho position to ameta position, or from a para position to :2. meta position. Forinstance, in the case of phenol-aldehyde varnish resins, one can prepareat least some in which the resins, instead of having onlytwo points ofreaction can have three, and possibly more points of reaction, withformaldehyde, or any other reactant which tends to form a rnethylol orsubstituted rnethylol group.

Apparently there is no similar limitation in regard to the resinsemployed in the aforementioned Bruson Patent 2,031,557, for the reasonthat one may prepare suitable resins from phenols of the kind alreadyspecified which invariably and inevitably would yield a resin having afunctionality greater than two in the ultimate resin molecule.

The resins herein employed are soluble in a non-oxygenated hydrocarbonsolvent, such as benzene or Xylene.

As pointed out in the aforementioned Bruson Patent 2,031,557, one of theobjectives is to convert the phenolaldehyde resins employed as rawmaterials in such a way as to render them hydrocarbon soluble, i. e.,soluble in benzene. The original resins of U. S. Patent 2,031,557, areselected on the basis of solubility in an oxygenated inert organicsolvent, such as alcohol or dioxane. It is immaterial whether the resinshere employed are soluble in dioxane or alcohol, but they must besoluble in benzene.

The resins herein employed as raw materials must be comparatively lowmolal products having on the average 3 to 6 nuclei per resin molecule.The resins employed in the aforementioned U. S. Patent No. 2,031,557,apparently need not meet any such limitations.

The condensation products here obtained, whether in the form of the freebase or the salt, do not go over to the insoluble stage on heating. Thisapparently is not true of the materials described in aforementionedBruson Patent 2,031,557 and apparently one of the objectives with whichthe invention is concerned, is to obtain a heatconvertible condensationproduct. The condensation product obtained according to the presentinvention is heat stable and, in fact, one of its outstanding qualitiesis that it can be subjected to oxyalkylation, particularly oxyethylationor oxypropylation, under conventional conditions, i. e., presence of analkaline catalyst, for example, but in any event at atemperature above100 C. without becoming an insoluble mass.

What has been said previously in regard to heat stability, particularlywhen employed as a reactant for 4 a preparation of derivatives, is stillimportant from the standpoint of manufacture of the condensationproducts themselves insofar that in the condensation process employed inpreparing the compounds described subsequently in detail, there is noobjection to the employing of a temperature above the boiling point ofwater. As a matter of fact, all. the examples included subsequentlyemploy temperatures going up to 140 to 150 C. If one were using resinsof the kind described in U. S. Patent No. 2,031,557 it appears desirableand perhaps absolutely necessary that the temperature be kept relativelylow, for instance, between 20 C. and,100 C., and more specifically at atemperature of to C. There is no such limitation in the condensationprocedure herein described for reasons which are obvious in light ofwhat has been said previously.

What is said above deserves further amplification at this point for thereason that it may shorten what is said subsequently in regard to theproduction of the herein described condensation products. As pointed outin the instant invention the resin selected is xylene or benzenesoluble, which differentiates the. resins from those employed in theaforementioned Bruson Patent No. 2,031,557. Since formaldehyde generallyis employed economically in an aqueous phase (30% to 40% solution, forexample) it is necessary to have manufacturing procedure which willallow reactions to take place at the interface of the two. immiscibleliquids, to wit, the formaldehyde solution and the resin solution, onthe assumption that generally the amine will dissolve in one phase orthe other. Although reactions of the kind herein described will begin atleast at comparatively low temperatures, for instance, 30 C., 40. C., or50 C., yet the reaction does not go to completion except by the use ofthe higher temperatures. The use of higher temperatures means, ofcourse, that the condensation product obtained atthe end of the reactionmust. not be heat-reactive. Of course, one can add an oxygenated solventsuch as alcohol, dioxane, various ethersv of glycols, or the like, andproduce a homogeneous phase. If this latter procedure is employed inpreparing the herein described condensations it is purely a matter ofconvenience, but whether it is nor not, ultimately the temperature muststill pass within the zone indicated elsewhere, i. e., somewhere abovethe boiling point of water unless some obvious equivalent procedure isused Any reference, as in the hereto appended claims, to the procedureemployed in the process is not intended to limit the method or order inwhich the reactants are added, commingled or, reacted. The procedure hasbeen referred to as a condensation process, for obvious reasons. Aspointed out elsewhere it is my preference to dissolve the resin in asuitable solvent, add the amine, and then add the formaldehyde as a 37%solution. However, all three reactants can be added in any order. I aminclined to believe that in the presence of a basic catalyst, such asthe amine employed, that the formaldehyde produces rnethylol groupsattached to the phenolic nuclei which, in turn, react with the amine. Itwould be immaterial, of course, if the formaldehyde reacted with theamine so as to introduce a rnethylol group attached to nitrogen which,in turn, would react with the resin molecule. Also, it would beimmaterial if both types of compounds were formed which reacted witheach other with the evolution of a mole of formaldehyde available forfurther reaction. Furthermore, a reaction could take place in whichthree different molecules are simultaneously involved although, fortheoretical reasons, that is less likely. What is said herein in thisrespect is simply by way of explanation to avoid any limitation inregard to the appended claims. Again it is to be emphasized that at theend of the oxyalkylati'on-step an esterification step follows.

Allowing for the fact that the nitrogen radical contains at least'onehydroxyl the condensate can be depicted ,the proviso that in eachterminal amino radical there subsequently.

have sufiicient hydrophilecharacter to at least meet the the obviouschemical equivalent or equivalent chemical addition of water. Such testis obviously the same for It is understood the reference in the heretoappended surface-active properties are readily demonstrated by producinga xylene-water emulsion. A suitable procedure is as follows: Theoxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50solution is then mixed with 1-3 volumes of water and shaken to producean emulsion. The amount of xylene is invariably sufiicient to reduceeven a tacky resinous product to a solution which is readilydispersible. The emulsions so produced are usually xylene-in-wateremulsions (oil- 10 in-water type) particularly when the amount ofdistilled water used is at least slightly in excess of the volume ofxylene solution and also if shaken vigorously. At times, particularly inthe lowest stage of oxyalkylation, must be at least one hydroxyl group 7one may obtain a water-in-xylene emulsion (water-in oil Thus, one canshow that oxyalkylation can take place 1 YP Whlch is pt tofeverse 011more vlgorous shaking not only at the phenolic hydroxyl but also at theamino and further dilutlon with Watergroup hydroxyl in the followingmanner: If in doubt as to this property, comparison with a moresatisfactorily for the present purpose in the following manner:

in which the characters have their previous significance, and n" is theinteger or a small whole number, with R R n R resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylationusing 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.Such resin prior to oxyalkylation has a molecular weight indicatingabout 4% units per resin molecule; Such resin, when diluted with anequal weight of xylene, will serve to illustrate the aboveemulsification test. In a few instances, the resin may not besufiiciently soluble in xylene alone but may require the addition ofsome ethylene glycol diethylether as described elsewhere. It isunderstood that such mixture, or any other similar mixture, isconsidered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surface-active characteristics As far as the use of theherein described products 4 in the products used in accordance with thisinvention. goes forthe purpose of resolving petroleum emulsions Theydissolve or disperse in water; and such dispersions of thewater-in'-oiltype, I prefer to use those which foam readily. Withborderline cases, i. e., those which show only incipient hydrophile orsurface-active property test setfforth in 'U. S. Patent No. 2,499,368dated March (sub-surface-activity) tests for emulsifying properties or7, 1950, to De Groote et al. In said patent such testself-dispersibility are useful. The fact that a reagent is foremulsification using a water-insoluble solvent, gencapable of producinga dispersion in water is proof that erally xylene, is described as anindex of surface activity. it i distinctly hydrophile. In doubtfulcases, comparison In the present instance the esters of the variousconcan b ad with the bnt l he l-f maldeh de re i densationproducts-maynot necessarily be xylene-soluble analog wherein 2 moles ofethylene oxide have been inalthough they are Xylene-soluble in a largenumber of troduced for each phenolic nucleus. instances. If Such o p sare not Xylene-801111918 The presence of Xylene or anequivalentwater-insoluble solvent may mask the point at which asolvent-free test can be madeby simply using some suitable solvent.product on mere dilution in a test tube exhibits selfpreferably awater-soluble solv nt s ch as hyl g y emulsification. For this reason,if it is desirable to de diethylether, a 10W molal alcohol, 3 mixture T0termine the approximate point where self-emulsification is pp p iProduct being fixamined and begins, then it is better to eliminate thexylene or equivn mix with the equal Weight of Xylene, followed y alentfrom a small potrion of the reaction mixture and test such portion. Insome cases, such xylene-free rethe reason that there Will be two phases(in vigorous ultantmay how or proper- Shaking and Surface activity makegits Presence manifasfties, whereas in presence of xylene such propertieswould not be noted. In other cases, the first objective indication ofhydrophile properties may be the capacity of the maincludcs such obvi sa a t terial to emulsify an insoluble solvent such as xylene. ItReference is Again made to Patent 2,499,363 is to be emphasized thathydrophile properties herein dated March 7, 19 to De Groom and Keiser-In said referred to are such as those exhibited by incipientselfimmediately flfmemeniioned Patsnt the following test emulsificationor the presence of emulsifying properties appears: v and go through therange of homogeneous dispersibility The. e is true in regard to theoxyalkylaied resins or admixture with water even in presence of addedwaterhefein Specified, Particularly in the lower Stage O Y- insolublesolvent and minor proportions of common elecalkylation;theso-calledsub-surface-active stage. The trolytes as occur in oil fieldbrines. r

in which for simplicity the formula just shown previously has beenlimited to the specific instance where there is only one hydroxyl in theamino radical. In the above formula R'fO is the radical of alkyleneoxide, such as the ethoxy, propoxy or similar radicals derived fromethylene oxide, propylene oxide, glycide or the like, and n is a numbervarying from 1 to 60, with the proviso that one need not oxyalkylate allthe available phenolic hydroxyl radicals or all the available hydroxylswhich are part of the amino radical. In other words, one need convertonly two hydroxyl radicals per condensate unit. It is immaterial Whetherthey are phenolic hydroxyls or hydroxyls which are part or" the aminoradical. Stated another way, it can be zero as well as a whole numbersubject to what has been said immediately preceding, all of which'willbe consideredin greater detail claims asto the use of xylene in theemulsification test that such emulsification tests employ a xylenesolution.

Stated another way, it is really immaterial whether a xylene solutionproduces a sol or whether it merely produces an emulsion.

Having describedthe invention briefly and not necessarily in itsmostcomplete aspect, the text immediately following will be a morecomplete description with specific reference to reagents and the methodof manufacture.

For convenience the subsequent text will be divided into six parts:

Part 1 is concerned with the general structure of the amine-modifiedresin condensates .and also the resin itself, with is used as a rawmaterial:

Part 2 is concerned with appropriate basic secondary monoaminescontaining at least one hydroxyl radical which may be employed in thepreparation of the herein described amine-modified resins orcondensates:

Part 3 is concerned with the condensation reactions involving the resin,the amine, and formaldehyde to produce the specific products orcompounds;

Part 4 is concerned with the oxyalkylation of the prod- I ucts describedin Part 3, preceding;

' Part 5 is concerned with the conversion of the polyhydroxylatedcompounds or reaction mixtures described in Part 4, preceding, intoacidic fractional esters bymeans of polycarboxy acids; and i I Part 6 isconcerned with the resolution of petroleum emulsions of the water-in-oiltype by means of the acidic.

fractional esters previously described.

In the subsequenttext, Parts 1, 2, and 3 appear in substantially thesame form as the text of the aforementioned co-pending application,Serial No. 288,743, filed May 19', 1952, and also in aforementionedco'pending application, Serial No. 301,804, filed July 30, 1952. Part 4is substantially the same as Part 4 as it appears in the last mentionedco-pending application. The text is so presented for bothvpurpose ofconvenience and comparison. Similarly, Part 5 is substantially the same'as'it appears in aforementioned co-pending application, Serial No.321,- 032, filed November 17, 1952.

PART 1 It is well konwn that one can readily purchase on the openmarket, or prepare, fusible, organic solvent-soluble, water-insolubleresin polymers of a composition approximated in an idealized form' bythe formula In the above formula n represents a small whole numbervarying from 1 to 6, 7 or 8, or more, up to probably '10 or 12 units,particularly when the resin is subjected to heating under a vacuum asdescribed in the literature. A limited sub-genus is in the instance oflow .molecular weight polymers where thetotal number of phenol nucleivaries from 3 to '6, i. e., n varies from 1 to 4; R represents analiphatic hydrocarbon substituent, generally an alkyl radical havingfrom 4 to 14 carbon atoms, such as a butyl, amyl, hexyl, decyl ordodecyl radicaL.

Where the divalent bridge radical is shown as being derived fromformaldehyde it may, ofcourse, be derived from any other reactivealdehyde having 8 carbon atoms or less. v

Because a resin is organic solvent-solublfi 1.06s not mean it isnecessarily soluble in any organic solvent. This is particularly truewhere the resins are derived from trifunctional phenols as previouslynoted. However, even when obtained from a difunctional phenol, forinstance para-phenylphenol, one'may obtain a resin which is not solublein anonoxygenated solvent, such as benzene, or xylene, but requires anoxygenated solvent such as a low molal alcohol dioxane, or diethylglycoldiethylether. Sometimes a mixture of the two solvents (oxygenated andnonoxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365,dated March 7, 1950, to DeGroote and Keiser.

The resins herein employed as raw materials must be soluble in anonoxygenated solvent, such as benzene or xylene. This presents noproblem insofar that all that is required is to makea solubility test oncommercially available resins, or else" prepareresins which are xyleneor benzene-soluble as described in aforementioned U. S. Patent No.2,499,365, or in U. S. Patent No. 2,499,368 dated March 7, 1950, toDeGroote and Keiser. In said patent there are describedoxyalkylation-susceptible, fusible, nonoxygenated-organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resinshaving an average molecular weight corresponding to at least 3 and notover 6 phenolic nuclei per resin molecule; said resin being difunctionalonly in regard to methylol-forming' reactivity; said resin being derivedby reaction between a difunctional monohydric phenol and an aldehydehaving not over 8 carbon atoms and reactive toward said phenol;

. said resin being formed in the substantial absence of trifunctionalphenols; said phenol being of the formula with two moles of formaldehydeandftwo moles of a basic nonhydroxylated secondary amine as-specified,following the, same idealized over-simplification-previously referredto, the resultant product mightbe illustrated thus: I

R R n'R The basic hydroxylated amine may be designated thus:

In conducting reactions of this kind one does not necessarily obtain ahundred per cent yield for obvious reasons. Certain side reactions maytake place. For

instance, 2 moles of amine may combine with one mole of the aldehyde, oronly one mole of the amine may combine with the resinmolecule, or evento a very slight extent, ifat all, 2 ,resinunits may 'combine'withoutanyamine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes onecan use a mole of aldehyde other than formaldehyde, such asacetaldehyde, propionaldehyde or butyraldehyde. The resin unit may beexemplified thus:

OH I OH OH URIIIURHI R R n R in which R' is the divalent radicalobtained from the particular aldehyde employed to form the resin. Forreasons which are obvious the condensation product obtained appears tobe described best in terms of the method of manufacture.

As previously stated the preparation of resins, the kind herein employedas reactants, is well known. See previously mentioned U. S. Patent2,499,368. Resins can be made using an acid catalyst or basic catalystor a catalyst having neither acid nor basic properties in the ordinarysense or without any catalyst at all. It is preferable that the resinsemployed be substantially neutral. In other words, if prepared by usinga strong acid as a catalyst, such strong acid should be neutralized.Similarly, if a strong base is used as a catalyst it is preferable thatthe base be neutralized although I have found that sometimes thereaction described proceeded more rapidly in the presence of a smallamount of a free base. The amount may be as small as a 200th of apercent and as much as a few 10ths of a percent. Sometimes moderateincrease in caustic soda and caustic potash may be used. However, themost desirable procedure in practically every case is to have the resinneutral.

In preparing resins one does not get a single polymer, i. e., one havingjust 3 units, or just 4 units, or just units, or just 6 units, etc. Itis usually a mixture; for instance, one approximating 4 phenolic nucleiwill have some trirner and pentamer present. Thus, the molecular weightmay be such that it corresponds to a fractional value for n as, forexample 3.5. 4.5 or 5.2.

In the actual manufacture of the resins I found no reason for usingother than those which are lowest in price and most readily availablecommercially. For purknow poses of convenience suitable resins arecharacterized 'in the following table:

TABLE I Mol Wt Ex. Position 3/ derived R n of resm N o. of R fromm 01 9W16 1a..-- Phenyl Para Formaldehyde. 3. 5 992. 5 2a Tertiary butyl. -dodo 3.5 882.5 3a-... Secondary butyl. 3. 5 882. 5 4a.... Cyclohexyl 3. 51,025. 5 5m... Tertiary amyl.... 3. 5 959. 5 6a...- Mixed secondary 3. 5805.5

and tertiary amyl. 7a---- Propyl 3. 5 805. 5 8a Tertiary hexyl. 3. 5 1,036. 5 9a..-. Octyl 3. 5 1,190. 5 10a..- Nonyl. 3. 5 1,267. 5 11a.DecyL... 3. 5' 1, 344. 5 12a Dodecyl. 3. 5 1, 498. 5 13a Tertiary butyl3. 5 945. 5 14a--- Terti 3. 5 1,022. 5 15ay --do 3. 5 1,330. 5 16aTertiary bntyl. do. Butyraldehyde. 3. 5 1,071. 5 17a Tertiary amy1 do do3.5 1,148.5 18a"- Nonyl o do 3. 5 1, 456. 5 19a- Tertiary butyl.- doPll'lopilonalde- 3.5 1, 008. 5 3. 5 1,085. 5 on 3. 5 1, 393. 5 Tertiarybutyl 4. 2 996. 6 23a Tertiary amyl. 4. 2 1,083. 4 24a- Nonyl 4.2 1,430. 6 25a Tertiary butyL 4. 8 1, 094. 4 26a Tertiary amyl 4. 8 1,189.627a Nonyl 4. 8 1, 570. 4

PART 2 As has been pointed out previously the amine herein employed as areactant is a basic hydroxylated secondary monoamine whose compositionis indicated thus:

in which R represents a monovalent alkyl, alicyclic, arylalkyl radicalwhich may be heterocyclic in a few instances as in a secondary aminederived from furfurylamine by reaction of ethylene oxide or propyleneoxide. Furthermore, at least one of the radicals designated by R musthave at least one hydroxyl radical. A large number of secondary aminesare available and may be suitably employed as reactatnts for the presentpurpose. Among others, one may employ diethanolamine, methylethanolamine, dipropanolamine and ethylpropanolamine. Other suitablesecondary amines are obtained, of course, by taking any suitable primaryamine, such as an alkylamine, an arylalkylamine, or an alicyclic amine,and treating the amine with one mole of an oxyalkylating agent, such asethylene oxide, propylene oxide, butylene oxide, glycide, ormethylglycide. Suitable primary amines which can be so converted intosecondary amines, include butylamine, amylamine, hexylamine, highermolecular weight amines derived from fatty acids, cyclohexylamine,benzylamine, furfurylamine, etc. In other instances primary amines whichhave at least one hydroxyl radical can be treated similarly with anoxyalkylating agent or, for that matter, with an alkylating agent suchas benzylchloride, esters of chloroacetic acid, alkyl bromides,dimethylsulfate, esters of sulfonic acid, etc., so as to convert theprimary amine into a secondary amine, Among others, such amines include2-a1nino-l-butanol, 2-amino2- methyl-l-propanol,2-amino-2-methyl-1,3-propanediol, 2- amino-2ethyl-1,3-propanediol, andtri-(hydroxymethyD- aminomethane. Another example of such amines isillustrated by 2-amino-4-m'ethyl-2-pentanol.

Similarly, one can prepare suitable secondary amines which have not onlya hydroxyl group but also one or more divalent oxygen linkages as partof an ether radical. The preparation of such amines or suitablereactants for preparing them has been described in the literature andparticularly in two United States patents, to wit, U. S. Patents Nos.2,325,514 dated July 27, 1943 to Hester, and

l1 2,355,337. dated August, 8., 19.44; to Spence-.; The latter patentdescribes typical haloalkyl etherssuch as CHaO 0213401 CHz-C Hz CH2H-CH20 02114002114131 or comparable compounds having two hydroxylatedgroups of different lengths as is (HOCH2QH2O CHICHaO CH CHQ) Otherexamples of suitable amines include benzylethanolamine andmethylethanolamine; also amines obtained by treatingcyclohexylmethylamine with one mole of an oxyalkylating agent aspreviously described; beta-ethylhexyl-butanolamine, diglycerylamine,etc. Another type of amine which is of particular interest because itincludes a very definite hydrophile group includes sugar amines such asglucamine, gelactamine and fructarnine, such as N-hydroxyethylglucamine,N-methylglucamine, N-hydrox-v yethylgalacetamine, andN-hydroxyethylfructamine.

Other. suitable amines may be illustrated by CHa H-0.0H2JJ.CH2OH IIIHHO.CH2C.CH2OH Ha 5 CH3.(|3.CH2OH NH ontbomon See, also, correspondinghydroxylated amineswhich can. be obtained. from rosin or similar rawmaterials and described in U. S. Patent No. 2,510,063,. dated June 6,1950, to Bried. Still other examples are illustrated by treatment ofcertain primary amines, such as the following,

with a mole of an oxyalkylating agent as described;

and 1,977,253, both dated October 16,, 1934, to Stallmann.

Among the reactants described in said latter patent are the following:

CHz-CHOHNH-CH3 PART 3 The products obtained by the herein describedprocesses represent cogeneric mixtures which are the result of acondensation reaction or reactions. Since the resin molecule cannot bedefined satisfactorily by formula, although it maybe so illustrated inan idealized simplification, it is difiicult to actually depict thefinal product of the cogeneric mixture except interms of the processitself.

Previous reference has been made to the fact that the procedure herein;employed .is comparable, in a general way, to that which corresponds tosomewhat similar derivatives made either from phenols as differentiatedfrom a resin, or in the. manufacture of a phenol-amine-aldehyde resin;or else from a particularly selected resin and an amine and formaldehydein the manner described in Bruson Patent No. 2,031,557 in order toobtain aheat-reactive resin. Since the condensation products obtainedare not heat-convertible and since manufacture is not restricted to asingle phase system, and since temperatures up to phcnoxyethylamine,phenoxypropylamine, phenoxyalphamethylethylamine, andphenoxypropylamine.

Other, procedures for production, of suitable compounds.

having a hydroxyl group-and asingle basic. amino nitrogen C. orthereabouts may be employed, it is obvious that the procedure becomescomparatively simple. Indeed, perhapsv no description .is,necessary overand above what has been said previously, in light of subsequentexamples. However, for purpose of clarity the following details areincluded.

A convenient piece of equipment for preparation of these cogenericmixtures is a resin pot of the kind described in aforementioned U. S.Patent No. 2,499,368. In most instances the resin selected is not apt tobe a fusible liquid at the early orlow temperature stage ofreaction ifemployedv assubsequently described; in fact, usually it is aptjto. be asolid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, I have found it convenient to use a solvent andparticularly onetwhich camber removed readily at a comparativelymoderate temperature, for instance, at 150 C. A suitable solvent isusually benzene, xylene, or a comparable petroleum hydrocarbon or amixture of such or similar solvents. Indeed, resins which are notsoluble except .in oxygenated solvents, or mixtures containing suchsolvents arenot here included as raw materials. The reaction can; beconducted in. Such, a way that the initial reaction, and perhaps the,bulk. of the reaction, takes place in a polyphase system. However, ifdesirable, one can use an oxygenated solvent such as a low-boilingalcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcoholscan be used or one can use. a. comparatively non-volatile solvent suchas dioxane or the diethylether of ethyleneglycoL, One can, also use amixture of benzene or xylene and such oxygenated solvents. Note that theuse of such oxygenated solvent, is not-required in the sense. that it isnot necessary to use an initial resin which is soluble only Jrteasonythat in most cases aqueous formaldehyde is employed, which maybe. they commercial product which is approximately 31%, or it may bediluted down to about 3.0% formaldehyde- Howe er, paraf rmaldehy c n beused, bu it sv m re difficul perhaps to add a solid mat ial; iIlStQad;of the. liquid solution and, everything else being equal, the latter isapt to be more economical. In any event, water is present as water ofreaction. If the solvent is completely removed at the end of theprocess, no problem is involved if the material is used for anysubsequent reaction. However, if the reaction mass is going to besubjected to some further reaction where the solvent may beobjectionable, as in the case of ethyl or hexyl alcohol, and if there isto be subsequent oxyalkylation, then, obviously, the alcohol should notbe used or else it should be removed. The fact that an oxygenatedsolvent need not be employed, of course, is an advantage for reasonsstated.

Another factor, as far as the selection of solvent goes, is whether ornot the cogeneric mixture obtained at the end of the reaction is to beused as such or in the salt form. The cogeneric mixtures obtained areapt to be solids or thick viscous liquids in which there is some changefrom the initial resin itself, particularly if some of the initialsolvent is apt to remain without complete removal. Even if one startswith a resin which is almost water-white in color, the products obtainedare almost invariably a dark red in color or at least a red-amber orsome color which includes both' an amber component and a reddishcomponent. By and large, the melting point is apt to be lower and theproducts may be more sticky and more tacky than the original resinitself. Depending on the resin selected and on the amine selected thecondensation product or reaction mass on a solventfree basis may behard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may bewater-insoluble or water-dispersible, or water-soluble, or close tobeing water-soluble. Water solubility is enhanced, of course, by makinga solution in the acidified vehicle such as a dilute solution, forinstance, a solution of hydrochloric acid, acetic acid, hydroxyaceticacid, etc. One also may convert the finished product into salts bysimply adding a stoichiometric amount of any selected acid and removingany water present by refluxing with benzene or the like. In fact, theselection of the solvent employed may depend in part whether or not theproduct at the completion of the reaction is to be converted into a saltform.

In the next succeeding paragraph it is pointed out that frequently it isconvenient to eliminate all solvent, using a temperature of not over 150C. and employing vacuum, if required. This applies, of course, only tothose circumstances where it is desirable or necessary to remove thesolvent. Petroleum solvents, aromatic solvents, etc., can be used. Theselection of solvent, such as benzene, xylene, or the like, dependsprimarily on cost, i. e., the use of the most economical solvent andalso on three other factors, two of which have been previouslymentioned; (a) is the solvent to remain in the reaction mass withoutremoval? (b) is the reaction mass to be subjected to further reaction inwhich the solvent, for instance, an alcohol, either low boiling or highboiling, might interfere as in the case of oxyalkylation); and the thirdfactor is this, (0) is an effort to be made to purify the reaction massby the usual procedure as, for example, a waterwash to remove thewater-soluble unreacted formaldehyde, if any, or a water-wash to removeany unreacted low molal soluble amine, if employed and present afterreaction? Such procedures are well known and, needless to say, certainsolvents are more suitable than others. Everything else being equal, 1have found xylene the most satisfactory solvent.

I have found no particular advantage in using a low temperature in theearly stage of the reaction because, and for reasons explained, this isnot necessary although it does apply in some other procedures that, in ageneral way, bear some similarity to the present procedure. There is noobjection, of course, to giving the reaction an opportunity to proceedas far as it will at some low temperature, for instance, 30 to 40 butultimately one must employ the higher temperature in order to obtainproducts of the kind herein described. If a lower temperature reactionis used initially the period is not critical, in fact, it may beanything from a few hours up to 24 hours. I have not found any casewhere it was necessary or even desirable to hold the low temperaturestage for more than 24 hours. In fact, I am not convinced there is anyadvantage in holding it at this stage for more than 3 or 4 hours at themost. This, again, is a matter of convenience largely for one reason. Inheating and stirring the reaction mass there is a tendency forformaldehyde to be lost. Thus, if the reaction can be conducted at alower temperature, then the amount of unreacted formaldehyde isdecreased subsequently and makes it easier to prevent any loss. Here,again, this lower temperature is not necessary by virtue of heatconvertibility as previously referred to.

If solvents and reactants are selected so the reactants and products ofreaction are mutually soluble, then agitation is required only to theextent that it helps cooling or helps distribution of the incomingformaldelyde. This mutual solubility is not necessary as previouslypointed out but may be convenient under certain circumstances. On theother hand, if the products are not mutually soluble then agitationshould be more vigorous for the reason that reaction probably takesplace principally at the interfaces and the more vigorous the agitationthe more interfacial area. The general procedure employed is invariablythe same when adding the resin and the selected solvent, such as benzeneor xylene. Refluxing should be long enough to insure that the resinadded, preferably in a powdered form, is completely soluble. However, ifthe resin is prepared as such it may be added in solution form, just aspreparation is described in aforementioned U. S. Patent 2,499,368. Afterthe resin is in complete solution the amine is added and stirred.Depending on the amine selected, it may or may not be soluble in theresin solution. If it is not soluble in the resin solution it may besoluble in the aqueous formaldehyde solution. If so, the resin then willdissolve in the formaldehyde solution as added, and if not, it is evenpossible that the initial reaction mass could be a three-phase systeminstead of a two-phase system although this would be extremely unusual.This solution, or mechanical mixture, if not completely soluble iscooled to at least the reaction temperature or somewhat below, forexample 35 C. or slightly lower, provided this initial low temperaturestage is employed. The formaldehyde is then added in a suitable form.For reasons pointed out I prefer to use a solution and whether to use acommercial 37% concentration is simply a matter of choice. In largescale manufacturing there may be some advantage in using a 30% solutionof formaldehyde but apparently this is not true on a small laboratoryscale or pilot plant scale. 30% formaldehyde may tend to decrease anyformaldehyde loss or make it easier to control unreacted formaldehydeloss.

On a large scale if there is any difiiculty with formaldehyde losscontrol, one can use a more dilute form of formaldehyde, for instance, a30% solution. The reaction can be conducted in an autoclave and noattempt made to remove water until the reaction is over. Generallyspeaking, such a procedure is much less satisfactory for a number ofreasons. For example, the reaction does not seem to go to completion,foaming takes place, and other mechanical or chemical difliculties areinovlved. I have found no advantage in using solid formaldehyde becauseeven here water of reaction is formed.

Returning again to the preferred method of reaction and particularlyfrom the standpoint of laboratory procedure employing a glass resin pot,when the reaction has proceeded as one can reasonably expect at a lowtemperature, for instance, after holding the reaction mass with orwithout stirring, depending on whether or not it is homogeneous, at 30or 40 C. for 4 or 5 hours,

or, t. the mos up to 1044' o rs. 1 hen; omplet he reaction by raisingthe temperature; up; to; 150? C.,, or thereabouts; as required. Theinitialv low temperature procedure can be eliminated or reduced tomerely the shortest period of timewhich avoids loss of amineorformaldehyde. At a higher temperature I use, a phaseseparating trap andsubject the mixture to reflux con-v densation' until the water ofreaction and the water of solution of the formaldehyde is eliminated; Ithen permit the temperature to rise to somewhere about. 100 C., andgenerally slightly above 1001-" and below 150 C., by eliminating thesolvent or part of the solvent so the reaction mass stays, within thispredetermined range. This period of heating and refluxing, after. thewater is. eliminated, is continued until. the reaction mass ishomogeneous and, then for one tothree hours longer. The removal of thesolvents'is conducted in a conventional manner in the same way as theremoval of solvents in resin manufacture as described in aforementionedU. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes I have invariablyemployed approximately one mole of the resin based on the molecularWeight of the resin molecule, 2 moles of the secondary amine and2'molesof formaldehyde. In some instances Ihave added a trace of causticas an added catalyst but have found no particular advantage in this. Inother cases I have used a slight excess of formaldehyde and, again, havenot found any particular advantage in this. In other cases I have used aslight excess of amine and, again, have not found any particularadvantage inso doing. Whenever feasible 1 have checked the completenessof reaction in the usual ways, including the amount of water. ofreaction, molecular weight, and particularly" in some instances havechecked whether or not the end-product showed surface-activity,particularly in a dilute acetic acid solution. The nitrogen contentafter removal of unreacted amine, if any is present, is another index.

In light of what has been said previously, little more need be said asto the actual'procedure employed for the preparation of the hereindescribed condensationproducts. The following example will serve by wayof illustration:

Example 1b The phenol-aldehyde resin is the one that has been identifiedpreviously as Example 2a. It was obtained from a paratertiary butylphenol and formaldehyde. The resin was prepared using an acid catalystwhich was completely neutralized at the end of the reaction. Themolecular weight of the resin was 882.5. This corresponded to an averageof about 3 /2 phenolic nuclei, as the value for n which excludes the 2external nuclei, i. e., the resin was largely-a mixture having 3 nucleiand 4 nuclei excluding the 2 external nuclei or 5 and 6 overall nuclei.The resin so obtained in a neutralstate had a light amber color.

882 grams of the resin identified as 2a preceding were powdered andmixed with 700 grams of xylene. The mixture was refluxed until solutionwas complete. Itwas then adjusted to approximately 30 to 35? C. and 210grams of diethanolamine added. The mixture was stirred vigorously andformaldehyde added slowly. The formaldehyde used was a 37% solution and160' grams were employed which were added in about 3 hours. The mixturewas stirred vigorously and kept within a temperature range of 30 to 45C. for about 21 hours. At the end of this period of time it wasrefluxed, using a phaseseparating trap and a small amount of aqueousdistillate withdrawn from time to time and the presence of unreactedformaldehyde noted. Any unreacted formaldehyde seemed to disappearwithin approximately 3 hours-after he efl x ng s r s umeshe dqr ftfo m:

aldehyde was no longer detectible the -phase separating trap wasset soasto eliminate all water, of solution; and:

reaction. After the water was eliminated part of the xylene was removeduntil the temperature reached about 150 C. The mass was kept at thishigher temperature for about 3% hours and reaction stopped. During thistime any additional water, which was probably water of reaction whichhad formed, was eliminated by means of the trap. The residual xylene waspermitted to stay in the cogeneric mixture. A small amount of the samplewas heated on a water bath to remove the excess xylene and the residualmaterial was dark red in color and had the consistency of a sticky fluidor a tacky resin. The overall reaction time was a little over 30 hours.In other instances it has varied from approximately 24 to 36 hours. Thetime can be reduced by cutting the low temperature period to about 3 to6 hours.

Note that in Table II following there are a large number of addedexamples illustrating the same procedure. In each case the initialmixture was stirred and held at a fairly low temperature (30 to 40 C.)for a period of several hours. Then refluxing was employed until theodor of formaldehyde disappeared. After the odor of formaldehydedisappeared the phase-separating trap was employed to separate out allthe water, both the solution and condensation. After all the water hadbeen separated enough xylene was taken out to have the final productreflux for several hours somewhere in the range of to C., orthereabouts. Usually the mixture yielded a clear solution by the timethe bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24examples in Table II.

PART 4 In preparing oxyalkylated derivatives of products of the kindwhich appear as examples in Part 3, the procedures employed aresubstantially the same as those conventionally used in carrying outoxyalkylations, and for this reason the oxyalkylation step will besimply illustrated by the following specific examples:

Example 10 The oxyalkylation-suseeptible compound employed is the onepreviously described and designated as Example The time regulator wasset so as to inject the ethylene oxide in approximately two hours andthen continue stirring for a half-hour or longer. The reaction wentreadily and; as a matter of fact, the oxide was taken up almostimmediately. Indeed the reaction was complete in less than an hour. Morespecifically it was complete in 45 minutes. The speed of reaction,particularly at the low pressure, undoubtedly was due in a large measureto excellent agitation and also to the comparatively high concentrationof catalyst. The amount of ethylene oxide introduced was equal in weightto the initial condensation product, to wit, 11.16 pounds. Thisrepresented a molal ratio of 25 moles of ethylene oxide per mole ofcondensate.

The theoretical molecular weight at the end of the reaction period was2232. A comparatively small sample, less than 50 grams, was withdrawnmerely for examination as far as solubility or emulsifying powerwasconcerned and also for the purpose of making some tests-on various oilfield emulsions.v 'The amount'withdrawn was so small thatno;,cognizance-of this factisineluded in the lar form in subsequentTables;3 and 4.

TABLE II 1 Max. Ex Resin Amt. Amine used and Strength of Solvent usedReactwn Reacmn "distill formaldehyde temp. time N used as. I amountSQIHI and mm and amt. 0 GI (hm) temp I lb 2a 882 Diethanolamine, 210 g 1Xylene, 700 g 22-26, 32 147,, 2b a 480 Diethanolamin'e, 105 g Xylene,450 g 21-23 I 28 150 3b 102 633 Xylene, 600 g 20-22 1361 145 411;" 2a441 Xylene, 400 g 2023 34 146 5b 1 5a 180 Xylene, 450 21-23 24 14161)... 1011 633 Xylene, 600 g 21-28 24 145 7b-- 2a 882 Xylene, 700 g2026 24 152 8b 5a 480 17% Xylene, 450 g 1 24-30 28 151 9b 100 633Xylene, 600 g 22-25 27 147 10b 13v, 473 Cyclohexylethanolamm 30%, 100 gXylene, 450 g 21-31 31 146 111)-- 14a 511 Cyclohexylethanolamine, 143 g37%, 81 g Xylene, 450 g 22-23 36- *148 12b; ,15a 665Cyclohexylethanolamtne, 143 g 37%, 81 g .1 Xylene, 550 g 20424 27 I 152I 1 m 2a 441 021150 0,11,00,11; r

' NH, 176 g 37%, 31 g Xylene, 400 g .1 21-25 24 150 HOCQH; I

141). 5a 480 C2H5O C2H4O C2114 I I NH, 176 g 37%, 81 g Xylene, 450 g20-26 26' 146 110C234 15b 9a 595 C2H5OC2H4OC2H4 NH, 176 37%," 51 g Xlene, 550 g 21-27 so 147 11002134 162'. 2a 441 HOC2Hl0C2H4OCzH4 I I N,192 37%, 81 g Xylene, 400 g -22 30 148' B00111,

17b 5a 480 HOCQHAOG2H4OC2H4 I I I N, 192 g 37% Xylene 20-25 1 2B 150 Inoogni 181).- 14a 591 HOOgH4OCzH4OCzH4 I I i N, 192 37%, 31 g Xylene,500 g 21-24 32 149 HOCzH 19b. 22a 498 HO 031140 CzH4O CzH4 I N, 192 g37%, 81 g Xylene, 450 g 22-25 32 153 HOCgH4 20b- 230 542 CHa(OO2H4)a I I7 206 g 0%, 1011 Xylene, 500 g 21-23 36 7 151 I HOO2H4 215-- 25a 54']OH3(OC:H4)3 3 I N, 206 g %,100 g- Xylene, 500 g 25-30 34 148 nooim22IL'- 2a 441 CH3(0C2H4)3 I ,206 2 30%, 100 g- Xylene, 400 g 22-23 31140 neon.

235-- 2611 595 Deeylethanolamine, 201 g 37%, 81 g Xylene, o 22-27 24 14524b 27a 391 Deeylethanolamine, 100 g 30%, 50 g Xylene, 300 g 21-25 26147 The size of the autoclave employed was 25 gallons. In innumerablecomparable oxyalkylations I have withdrawn a substantial portion at theend of each step and continued oxyalkylation on a partial residualsample. This was not the case in this particular series. Certainexamples were duplicated as hereinafter noted and subjected tooxyalkylation with a different; oxide. 1 I

- Example 20. This example simply illustrates the further oxyalkylationof Example 10, preceding.- As previously stated, the

' oxyalkylation-susceptible compound, to wit, Example 1b,

present at the beginning of the stage was obviously the same'as at theend oi the .prior stage (Example 10), to wit, 11.16 pounds. The amountof oxide present in the initial step was 11.16 pounds, the amount ofcatalyst remained the same, to wit, one pound, and the amount of solventremained the same. The amount of oxide. added was another 11.16 pounds,all addition of oxide in these various stages being based on theaddition of this particular amount. Thus, at the end of theoxyethylation step the amount of oxide added was a total of 22.32 poundsand the molal ratio of ethylene oxide to resin condensate was 50.8 to 1.The theoretical molecular weight was 3348.

The maximum temperature duringfthe operation was C. to C. The maximumpressure was in the range of '15 to 20 pounds. The time period wasonehour;

. Example 30 I The oxyalkylation proceeded in the same manner describedin Examples 10 and 2c. There was no added solvent and no added catalyst.The oxide added was 11.16 pounds and the total oxide at the end of theoxyethylation step was 33.48 pounds. The molal ratio of oxide tocondensate was 76.2 to 1. Conditions as far as temperature and pressureand time were concerned were all the same as inExamples 1c and 2c. Thetime period was somewhat longer than in previous examples, to wit, 2hours.

weight at the end of thereaction period was 5580; "The molal'ratio ofoxide to condensate was 101,6 to 1. ,Con-

ditions as far as temperature and pressure were concerned were the sameasin previous examples. The time period was slightly longer, to wit, 3/2 hours. The reaetion unquestionably began to slow up somewhat.

Example The. oxyethylation continued withjthe introduction of another11.16 pounds of ethylene oxide. No more solvent was introduced but .3:poundicaustic soda was-added. The theoretical molecular weight at theend of the agitation period was 6696, and the molal ratio ofoxide toresin condensate was 127 to 1. The time period, however, dropped to 1%hours. Operating temperature and pressure remained the same as in theprevious example.

Example 6;

The same procedure was followed as in; the previous examples exceptthat'an added A pound of powdered caustic soda was introduced to speedup the reaction. The amount of oxide added was another. 11.16 pounds,bring; ing the total oxide introduced to 66.96 pounds. The temperatureand pressure during this period were the same as before. There was noadded catalyst and also no added solvent. The time period was 2 /22.hours.

- Example 70 The same procedure was followed as in the previous sixexamples without the addition of more caustic or more solvent. Thetotal: amountt of oxide introducedat the end of the period was 78.12pounds. The theoretical molecular weight at the end of the oxyalkylationperiod was 8928. The time required for the oxyethylation was a bitlonger than in the previous step, to wit, 3 hours.

Example 80 This was the final oxyethylation in this particular series.There wasno added solvent and noadded catalyst. The total amount ofvoxide added at the end of this step was 89.28 pounds; The theoreticalmolecular weight was 10,044. The molal ratio of oxide to resincondensate was 293.2 to one. Conditions as far as temperature andpressure were concerned were thesame as in the previous examples and thetime required for oxyethylation was 4 hours. 1

The same procedure as. describedin the, preyiousexamples was employed inconnection with a number of the other condensates described previously.All these data have been presented in tabular form in a series of v fourtables, Tables. III and:,IV, V. andiVI.

In substantially every case a ZS-gallon autoclave was employed, althoughin some instances the initial oxyethylation was started in;a -gallon.autoclave and then transferred to a -gallon autoclave. This is imrnarial l th npsnesitq a t e of qn eai nsa nly- T e.

solv nt: u ed. in];a 11 v cases w sx e e, h at t used w s nelyp wd rpaustis oda.

Re eninanow Q ab ss I nd t l ended.

a -c mpoun s h ou h. 4%. e e. bt ined.- by. he.

useof ethylene oxide, whereas 41c through 80c wereoba u d' yih usqq p ol'sueox de a Th n. f renc o. ab e IIf t s follows.

The example number of each compound is indicated in thefirstcolumn.

The, identity. of the oxyalkylation susceptible com- POUnd, towit, the.resin. condensate, is. indicated in the second column;

o e, not d. as

Theamount of condensateis shown in the third column. Assumingthatethylene oxide alone. is employed, as happens to bethe case in Examples.10 through.40c, the. amount of-:- oxidev present in the. oxyalkylationderivative xya ky at on,- step,

is hlank; i r 6thcolurnn showsthe amount of.powde red.caustie soda usedas a catalyst, and the 7th column shows'the amount of solvent employed.I v The 8th. column canibe 'gnoredjwherea single oxidewas employed. I

The 9th column shows the, theorcticalmolecular weightf at the end of.the oxyalkylation period:

h 0t m tat s he. mo nt present in the reaction mass. at; the endof theperio s. As pointed out. previously, in this particular seriesth'e,amount of reactiommass. withdrawn for examination was so small that itwas ignored andfor this reason the resin, condensate in' column 10coincides with the figure in column 3! Column" llshows the amount ofethylene oxide em- 7 ployed in the reaction mass. at; the. endo f; the;particular period.

Column 12 can'be ignored insofar that no propylene oxidewas employed. a

Column 13' shows the catalyst, at the; end of the reac;

tion period- 1 Column, 14. shows the amount of solvent at the end of thereaction period. 7

Column 15 shows. ihfI11Q1alifatiQ;0f$ ethylene oxide to condensate.

Column 16' can be ignored for the reason that no propylene oxide wasemployed. 1

7 Referring now to Table V I, It is to be notedthat the. first columnrefers to Examples 10, 2c, 30, etc.

The second"column gives the maximum temperature employed during theoxyalkylation step and: column givesthemaximum pressure.

The fourth column gives the time period employed.

The last three columns show solubility tests by shaking a small amountof the compound, including the solvent present, with several volumes ofwater, xylene and kero-. sene. Itsqmetimeshappens that although xylenein comparatively small amounts will dissolve in the concentratedmaterial, when the concentrated material in turn is diluted with xyleneseparation takes place.

Referring to Table IV, Examples 41c through 800 are the counterparts ofExamples 10 through 400, except that the oxide employed is propyleneoxide instead of ethylene oxide. Therefore, asexplained.previously, fourcolumns. are blank, to wit, columns 4, 8, 11 and 15.

Referenceis now made to Table V. It is to be noted these compounds aredesignatedby dnumbe rs, 1d, 2d, 3d, etc., through and inc'ludingy32d'.They are derived,

in t rn from compoundsin the c series, for example,

c, 39c, 53c-and 62c. Thesecompounds involve the use of both ethyleneoxide and'propylene oxide. Since compounds 10, through-40'c were;obtained; by the useof" ethylene oxide, it is obvious that'thoseobtained from 35c, and 390, involve the'use of ethylene oxide first, andpropylene oxide afterward. Inversely, those compounds. obtained from 53cand=62c obviously came from a prior. series inwhich propylene oxidewasusegl first. i

, In the preparation of-this series indicated-by the small letter..'d,-"as 1d,"2'd, 3d; etc.,the initial c series-such as 356-390, 530,and' 62e, were 'duplicatedand the oxyalkylation stopped at the pointdesignated instead ofbeing carried further as may have-been the case inthe original hea; oxyal latio proceed y using the second oxideasindicatedby the previous expla. 1 atiom t wi .pr ny neoxide n 1dthrouz 6d. and ethyleneoxide in. Uzi-through 3241; inclusive. i

,In examining the table beginning-with 1d, it will-be noted; that; theinitialproduct, i. e., 35c, consisted of the reactionproduct. involving.171.16. pounds of the; resin condensate, 16.74 poundsoi -ethylene oxide,1.0 poundof condensate,

the third It is to be noted that reference to the catalyst in Table Vrefers to the total amount of catalyst, i. e., the catalyst present fromthe first oxyalkylation step plus added catalyst, if any. The same istrue in regard to the solvent.

then use ethylene oxide, and then go back to propylene oxide; or, onecould use a combination in which butylene oxide is used along witheither one of the two oxides just mentioned, or a combination of both'of them.

Reference to the solvent refers to the total solvent present, The colorsof the products usually vary from a reddish i. e., that from the firstoxyalkylation step plus added amber tint to a definitely red, and amber.The reason solvent, if any. r is primarily that no effort is made toobtain colorless In this series, it will be noted that the theoreticalmoresins initially and the resins themselves may be yellow, lecularweights are given prior to the oxyalkylation step amber, or even darkamber. Condensation of a nitrogand after the oxyalkylation step,although the value at enous product invariably yields a darker productthan the the end of one step is the value at the beginning of theoriginal resin and usually has a reddish color. The solnext ste exceptobviously at the very start the value vent empl ye if Xyl n s nothing tothe color but depends on the theoretical molecular Weight at th end onemay use a darker colored aromatic petroleum solvent. of the initialoxyalkylation step; i. e., oxyethylation for oXyalkylatioIl generallytends to yi d lighter Colomd 1d through 1611, and oxypropylation for17dthrough 32d. products and the more oxide employed the lighter the Itwill be noted al o that unde the molal atio th color of the product.Products can be prepared in which values of both oxides to the resincondensate are included. the final @0101 is a lighter amber h a reddisht- The data given in regard to the operating conditions Such productscan be decolorized by the use of clays, is substantially the same abefor and appears i Tabl bleaching chars, etc. As far as use indemulsification is VI. 20 concerned, or some other industrial uses,there is no jus- The products resulting from these procedures may confit n for the 60st of bleaching the Product tain modest amounts, or havesmall amounts, of the sol- If the oxyalkylated derivatives were not usedin subvents as indicated by the figures in the tables, If desir dsequent esterification reactions, then alkalinity, whether the solventmay be removed bydistillation, and particudueto an amino nitrogen atomor added catalyst, would larly vacuum distillation. Such distillationalso may re-' be i m t a for y P P For-esterificationit is move tracesor small amounts of uncombined oxide, if I preferable that thealkalinity be eliminated in anyone present and volatile under theconditions employed. of a number of ways; ((1) add an acid equivalent tobe Obviously, in the use of ethylene oxide and propylene added catalyst;([1) convert the catalystinto'sodium chlooxide in combinationone neednot first use one oxide and ride and the amine radical into ahydrochloride; or (c) 3 then the other, but one can mix the two oxidesand thus use an excess of the polycarboxy reactant even though a I,obtain what may be termed an indifferent oxyalkylation, small percentageis wasted. All this is discussed indei. e., no attempt to selectivelyadd one and then the tail in the next section. More careful examinationof other, or any other variant. r this type of material can be made bymethods employing Needless to say, one could start with ethylene oxidethe well known Karl Fischer reagents, as described in, and then usepropylene oxide, and then go back to eth- Aquametry, Smith and Mitchell,Jr. Interscience Pubylene oxide; or, inversely, start with propyleneoxide, lishers, New York, 1948.

TABLE III Composition before Composition at end Molalratio o-s' Eth 1P' 1. c t s 1 Th Theo. o-s* Ethyl Pro 1. Catas61- gf cmpd oxid e, 051121, 595?, ve it, 111:1? mol. cmpd., oxide, 5x152, lyst, vent, EggsEgg: N0 lbs. lbs. lbs. lbs. lbs. wt. wt. lbs. lbs. lbs. lbs. lbs. toresmtore/Sm condencondensate sate 'Oxyalkylation-susceptible.

TABLE VI TABLE VI-Cntinued s l Max. Max. Time Solubility EX. Max. Max.Time, 011111111153 a, p No. i presv hrs.

0. p.s.i. 5 C. p. s. 1. W t X 1 K Water Xylene Kerosene a er y eneerosene 125-135 15-20 3 Insoluble 250k 130435 510 Insoluble.

125-135 15-20 A Emulsifiable and. 130-135 5-10 1 Do.

125-135 15-20 Sol ble 1311-135 l0 1% D0.

125-135 15-20 2911- 130435 10 3% Dispersible.

125-135 -20 3011. 130-135 5-10 3 Insoluble.

125-135 15-20 32d. 130-135 510 2% Do.

125-130 15-20 0 As previously polnted out, the present invention is tg81 38 4 concerned with acidic esters obtained from the oxyalkyl- 1125-13015-20 a ated derivatives described in Part 4 immediately preced- 125.1301H5 ing, and polycarboxy acids, particularly dicarboxy acids 125-13010-15 /y such as adipic acid phthalic acid, or anhydride, succinic Kg 2d acid, diglycolic acid, sebacic acid, azelaic acid, aconitic 1125-13010-15 I III" acid, maleic acid or anhydride, citraconic acid or an-{3533 3 hydride, maelic acid or anhydride adducts, as obtained 130-13515-20 by the Diels-Alder reaction from products such as maleic hi8anhydride, and cyclopentadiene. Such acids should be 30135 15- 0heat-stable so they are not decomposed during esterifica- 138 tion. Theymay contain as many as 36 carbon atoms 130-135 15-20 as, for example,the acids obtained by dimerization of 1 8 unsaturated fatty acids,unsaturated monocarboxy fatty acids, or unsaturated monocarboxy acidshaving 18 carbon atoms. Reference to the acid in the hereto appendedDisligrsiblev 4O sarily must yield at least three react1ve hydroxylradications, Serial Nos. 321,931, 321,033, 321,034, and 321,-

D0. 035, invariably there must be at least two basic nitrogen .125-1g015-20 D Do.b1 atoms. 125-1 0 15-20 ispersi e. 125 130 1H0 so uble It ismy preference always to add enough of a strong D0. acid, such ashydrochloric acid or sulfuric acid, so as to be stoichiometricallyequivalent to the basicity of the hy- 125-130 15-20 Inso l b'le. droxyreactant. Also, I prefer to use a slight additional 125F130 1H0 8:excess and if need be suflicient to. combine with the ni- I125-130 15-20Do. trogen basicity of the reactant, and if needed an excess igjgg 3;over and above this amount. At the worst, if there is '125-130 15-20 perb e. no excess, some of the polycarboxy acid reactant may 125430 1H0Soluble be wasted in a neutralizing reaction rather than an esteri-125-130 15-20 Insoluble. 125-130 15-20 D0. fication reaction. Such saltmay, however, convert into 58 gig B3; an ester. However, it is mypreference to use the oxy- 125-130 15-30 Do. alkylated derivatives inwhich the original resin condeni ?g sate contributes a comparativelysmall fraction and thus 25-130 15-20 80111 1 111. the basicity may initself either be insignificant or com- 3523 8: paratively small from aneutralization standpoint. With 5 538 gi these facts in mind one canprepare the esters in substan- 1125430 2H0 Insoluble. tially the sameway as if one were esterifying polyhyg8: droxylated reactants free fromany nitrogen atom, par- 25-130 25-3 D I ticularly any basic nitrogenatom.

gig claims obviously includes the anhydrldes or any other 125430 1H0obvious equivalents. My preference, however, is to use -130 15-20 01carbox acids an articularl dicarbox cids hav- 125-130 15-20 Insoluble. Py d p y y a 125-130 15-20 Dispersible. mg not Car atOmS- 3 35 In thepresent instance the polyhydroxylated react-ants 125.130 15.20 have atleast two or more hydroxyl radicals. Indeed, 125430 1520 assuming theresin unit has three or more phenolic hy- 125-130 15-20 Do. 3 125430 1H0droxyls which always would be true, oxyalkylauonneces- 125-130 25-35Insoluble.

12543 25-35 cals except in the very early stages or very low limit of125430 25-35 oxyalkylation as described in the preceding section. If125-130 25-35 Do. I 125- 21 glyclde or methylglyclde were used thenumber of hy- 2535 droxyl radicals would be larger. Since the phenolicresin. 125-130 25-35 Do. 130-135 5-10 Insoluble, itself may have severalphenolic hydroxyls there is fur- 130435 540 Disperslble- 45 theropportunity for a multiplicity of hydroXyl-radicals in 130-135 5-10 Do.130-135 5 10 s l the reactant which serves as an alcohol in theester1fica- 130435 tion step. The presence of a basic nitrogen atom in-130-135 5-10 Do.

130-135 5-10 Do. volves some added compllcatlon due to its 1nherentsalt- 130-135 5-10 Do.

EH35 1H0 Insoluble. formlng character. If several basic nltrogen atoms125-135 15-20 h V 0. 50 happened to be present 1n a polyhydroxylatedreactant, 15-20 Dlsperslblethe same would be true to a greater degree.In any con- 125-135 15-20 Soluble. 125-135 15-20 Do. densate of thegeneral type hereln described, and also 1n 5138 %g: the type ofcondensate described in my co-pending appli- As stated in U. S. PatentNo. 2,602,060 dated July 1, 1952, to De Groote, the production ofesters, including acidic esters (fractional esters) from polycarboxyacids and glycols or other hydroxylated compounds is well known.Needless to, say, various compounds may be usedsuch as the low molalester, the anhydride, the acyl chloride, etc. However, for purpose ofeconomy it is customary to use either the acid or the anhydride. Aconventional procedure is employed. On a laboratory scale one can employ.a resin pot of the kind described in U. S. Patent No. 2,499,370, datedMarch 7, 1950, to De Groote and Keiser, and particularly with one moreopening, to permit the use of a porous spreader if hydrochloric acid gasis to be used as a catalyst. Such device or absorption spreader consistsof minute alundum thi'mbl'es which are connected to a glass tube. Onecan add' a sulfonic acid such as paratoluene sulfonic acid as' acatalyst There is some objection to this because in some instances thereis some evidence that this acid cata- 'lyst tends to decompose orrearrange polyoxyalkylated compounds, and particularly likely to do soif the esterification temperature is too high. In the case ofpolycarboxy acids such as diglycolic acid, which is strongly acidic,there is.no need to add any catalyst.

In the case" of highly oxyalkylated' compounds, where nitrogen basicitycanbe ignored, or almost ignored, the use of hydrochloric gas has oneadvantage over paratoluene sulfonic acid and that is that at the end ofthe reaction it can be removed by flushing out with nitrogen, whereasthere is no reasonably convenient means available of removing theparatoluene sulfonic acid or other sulfonic acid employed. Ifhydrochloric acid is employed one need only pass the gas through at-anexceedingly slow rate so as to keep the reaction mass acidic. Onlyatrace of acid need be present. I have employed hydrochloric acid gasor'the aqueous acid itself to eliminate the initial basic material. Mypreference, however, is to use no catalyst whatsoever and to insurecomplete dryness of the oxyalkylated amine-modified phenolaldehyde resinas described in the. final procedure just preceding Table VH.

The productsobtained in Part 4, preceding, may contain a basic catalystusing highly oxyalkylated compounds, as a general procedure Ihave addedan amount of halfconcentrated hydrochloric acid considerably in excessof what is required to neutralize the residual catalyst. The mixture isshaken thoroughly and allowed to stand overnight. It'is then filteredand refluxed with the xylene.

present until the water can be separated in aphase-separating trap. Assoon as the product is substantially free.

from water the distillation stops- This preliminary step can be carriedout in the flask to be used for esterification- If there is any furtherdeposition of sodium chloride during v the reflux stage,,nee dless tosay, a second filtration;

may berequired. I

In any event, the product resulting from this pre-treab. ment is apt tobe neutral or basic and particularly slightly basic. My preference, aspointed .out previously, is that the product be neutralor slightlyacidic. Oddly enough, if all the basicity is dueto a'basic'nitrogen atomor more than one basic nitrogen atom since the resin condensate mustinvariably and inevitably have at least two basic nitrogen atoms,I havefound that in the stages ofmodest or heavy oxyalkylation the finalproduct indicates that the basicity has been greatly reduced, possiblydue to the hydroxylation or some other effect. Compare, for exampin, thereduced basicity of triethanolamine with that of ammonia. As previouslynoted, at the worse if 'all the catalyst has been removed or neutralizeda little of the polycarboxy reactant may be lost.

Considering theresin condensates which. aresubjected to oxyalkylation,not only in the present application but also in the, four, co-pendingapplications, Serial Nos.. 321,031, 321,033, 321,034, and 321,035, it.is apparentthe situation becomesfurther complicated by. the fact that:

If a little more acid is used it may even be acidic.

event, is perfectly acceptable for esterification in the.

in regard to esterification applied with equal force and efiectsubstantially to all hydroxylated compounds described, not only in thisapplication but also in the four 3 co-pending applications notedimmediately above.

In any event, such, oxyalkylated derivative described in Part 4 is thendiluted further with sufficient xylene,

decalin, petroleum solvent, orthe. like, so that one has obtainedapproximately a 65% solution. To this solution there is added apolycarboxylated reactant, as previously described, suchasphthalicanhydride, succinic acid, or anhydride, diglycolicacid, etc., in theratio of one-mole of polycarboxy reactant for each available hydroxyl'radical. The mixture is refluxed until esterification is complete asindicated by elimination of water or drop in carboxyl value. Needless tosay, if one produces a halfester from an anhydride such as phthalicanhydride, no

water is eliminated. However, if it is obtained from diglycolic acid forexample, water is eliminated. All such procedures are conventional andhave been so thoroughly described in the literature that furtherconsideration will be limited to a few examples and a comprehensivetable.

Other procedures for eliminating the basic residual catalyst, if any,can be employed. Forexample, the oxyalkylation can be conducted inabsence of a solvent or the solvent removed after oxypropylation. Suchoxyalkylated end-product can then be acidified with just enoughconcentrated hydrochloric acid to just neutralize the residual basiccatalyst. To-thisproduct one can then add a small amountof anhydroussodium sulfate (sufficient in quantity to takeup any water thatispresent) and then subjectthe mass to. centrifugal force so as to.eliminate the dehydrated sodium; sulfateandprobably the sodium chlorideformed. The; clear, somewhat viscous, straw-colored amber liquid, orreddish-amber liquid, so obtained may contain a small amount of sodiumsulfate or sodium chloride, but in any manner described, subject to whathas been said previously in regard. to basicity due to the basicnitrogen atoms present.

It is. to-be pointed out that the products here described are notpolyestersin the sense that there is a plurality of both hydroxyreactant radicals and acid radicals; the product is characterizedbyhaving only one hydroxy reactant radical;

i In some. instances, and in fact, in many instances, I have foundthatin spite of the dehydrationmethods employed above a mere trace of waterstill cQmesthrough, and that this mere, trace of jwater certainlyinterferes with the acetyl or hydroxyl: value determination, at leastwhen a number of conventional procedures are used and may retardesterification particularly Where there is no sulfonic acid orhydrochloric acid present as a catalyst. Therefore, I have preferred to.use the following procedure: I have employed about 200 grams of thehydroxylated compound as described in;Part 4, preceding; I have addedabout 200 grams. of benzene, and then refluxed this mixture in theglassresin pot using a phase-separating trap until the benzenecarriedout. all the water present as water of solution or the equivalent.Ordinarily this refluxing temperature is apt to be in the neighborhoodof to possibly C. When all this water or moisture has been removed Ialso withdraw approximately 100 grams or a little less benzene and thenadd the required amount of a they were almost completely aromatic incharacter.

29 Typical distillation data in the particular type I have employed andfound very satisfactory is the following: I. B. P., 140 50 ml., 242 C.ml., 200 C. 55 ml., 244 C.

30 higher, for 8 hours, after which it has been found that in almostevery instance reaction is complete. Water, it formed, is separated bythe usual trap arrangement. Of course, when anhydride is used there islittle or no forma- 10 ml., 209 c. 60 ml., 248 c. 5 Of Wale E l 1 1111.,215 c. '65 1111., 252 0. 9 e ml., 216 C. 70 ml., 252 C. The hydroxylatedcompound was the one previously ml., 220 C. 75 ml., 260 C. identified asExample 70. The amount employed was 200 ml., 225 C. 80 ml., 264 C. 10grams. The amount of xylene was 210 grams. The polyml., 230 C. 85 ml.,270 C. carboxy reactant was diglycolic acid. The amount emml., 234 C. 90ml., 280 C. ployed was 12 grams. The maximum reflux temperature ml., 237C. ml., 307 C. was about 164 C. The time of esterification was 8 hours;After this material is added, refluxing is continued and, the amount ofWater Was grams- The Same of course, is at a high temperature, to wit,about 160 to 15 Pmcedure was followed a number of other examples, 170 C.If the carboxy reactant is an anhydride, needless all of WhlCl'l areincluded 1n Table VII immediately to say, no water of reaction appears;if the carboxy reactfollowing.

TABLE VII Amt. 0i Amt of Max. T. Theo. hyd. Solvent esterifiof F-Ex. No.of Ex. No. Theo.m.w. p ycarb. estenfi- Water acid ester of Cmpd. of hyd.val. cmpd. Polycarboxy reactant reactant, (xylene), cation, cation, outcc.

of h. c grs. grs grs. temp., hr

76 8, 928 25. 1 200 Diglycolic acid 12. 0 210. 4 164 3 76 928 25.1 200P11016116 anhydride 13. 3 213. 3 169 8 7c 8, 928 25.1 200 Maleicanhydride 8. 79 208. 0 165 8 7c 8, 928 25. 1 200 ACODitiC aeid 15. 6214. 0 170 8 8C 10, 044 22. 3 200 Dig1y661i6 961d. 10. 7 209.3 165 8 8610,044 22. 3 200 1011115116 anhydr 11.8 211. 8 163 8 8C 10, 044 22. 3200 Maleic anhydride 7. 8 207.8 168 8 8C 10, 044 22.3 200 Adipic 561d11. 6 210. 2 167 s 156 10,000 22. 45 200 D1 1 66116 acid.-- 10.7 209.3167 8 10,000 22.45 200 Phthulic 51111 611116 11. 85 211.8 170 3 15C 10,000 22. 45 200 M61616 auhydrlde- 7. 84 207. s 163 s 156 10,000 22. 45200 Succinic anhydride. 8.0 208. 0 164 s 166 11, 250 19. 95 200Diglycolic 661d... 9. 5 208. 2 163 3 11,250 19. 95 200 P11015116anhydride- 10.5 210. 5 171 8 160 11,250 19. 95 200 M81810 anhydride. 6.95 206. 95 170 s 166 11,250 19. 95 200 466111116 acid... 12. 35 211. 0 8456 7, 812 28. 8 200 Diglycolic 6610.. 13. 73 211. 9 165 8 456 7, 81228. 8 200 Phtha116 9J1hyd1lde 15. 2 215. 2 172 s 456 7, 812 28.8 200M61616 111111 111106. 10. 0' 210. 1 168 8 456 7, 812 28.8 200 Adlpic801d. 15. 0 213. 2 8 536 8, 750 25. 7 200 Diglycolie acid. 12.25 210. 6170 8 536 8,750 25. 7 200 Phthalio anhydr1de 13. 55 213. 6 167 8 5368,750 25.7 200 M61616 51111 61106" 8.96 209.0 163 8 531.- 8, 750 25. 7200 Summit: anhydride,. 9. 15 209. 0 168 8 21d 12, 500 17. 95 200Diglycolic 116111.- 8. 59 207 168 8 21d 12, 500 17. 95 200 P11019116anhydrid 9. 49 209 164 8 21d 12, 500 17.95 200 Maleio anhydride 6. 26206 166 3 21d 12, 500 17.95 200 ACOILltlC 661d. 11. 15 210 172 8 22d 13,125 17.1 200 Diglycolic acid. 8. 15 207 169 3 22d 13, 125 17. 1 200 11111111116 anhydrid 9. 0 209 170 8 22d 13,125 17.1 200 M61616anhydride,. 5. 96 206 168 8 2211 13,125 17. 1 200 Adipic twid 8.89 208163 8 2312 13,750 16. 35 200 Diglyeolic acid. 7. 79 206. 7 163 8 23d13,750 16. 35 200 Phthalic anhydndes. 6 208. 6 170 8 23d 750 16 35 200Malele anhydrrde..- 5. 7 205. 7 160 8 2311 13,750 16 35 200 Succinicanhydrrde. 5. 81 205.8 170 8 24d 15,000 14 95 200 Diglyoolic 6616...-..7.14 206.2 165 8 24d 15,000 14 95 200 Phfllnlic anhydrrde. 7. 89 208 1688 2411 15,000 14. 95 200 M61616 anhydride 5. 21 205 166 8 246 15,000 .95200 A66111ti6 801d 9. 28 208.3 169 8 ant is an acid, water of reactionshould appear and should PAR 5 be eliminated at the above reactiontemperature. If it is not eliminated, I simply separate out another 5 to10 cc. of benzene by means of the phase-separating trap and thus raisethe temperature to or C. or even to 200 C., if need be. My preference isnot to go above 200 C.

The use of such solvent is extremely satisfactory, provided one does notattempt to remove the solvent subsequently except by vacuumdistillation, and provided there is no objection to a little residue.Actually, when these materials are used for a purpose such asdemulsification the solvent might just as well be allowed to remain. Ifthe solvent is to be removed by distillation, and particularly vacuumdistillation, then the high boiling aromatic petroleum solvent mightwell be replaced by some more expensive solvent such as decalin or analkylated decalin which has a rather definite or close range boilingpoint. The removal of the solvent, of course, is purely a conventionalprocedure and requires no elaboration.

' Merely by way of illustration; the following examples use a simpleprocedure, to wit, the hydroxylated compound is mixed with an equalweight of xylene and refluxed at approximately 165 to 170 C., orsomewhat Conventional demulsifying agents employed in the treatment ofoil field emulsions are used as such, or after dilution with anysuitable solvent, such as water, petroleum hydrocarbons, such asbenzene, toluene, xylene, tar acid oil, cresol, anthracene oil, etc.Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethylalcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexylalcohol, octyl alcohol, etc., may be employed as diluents. Miscellaneoussolvents such as pine oil, carbon tetrachloride, sulfur dioxide extractobtained in the refining of petroleum, etc., may be employed asdiluents. Similarly, the material or materials employed as thedemulsifying agent of my process may be admixed with one or more of thesolvents customarily used in connection with conventional demulsifyingagents. Moreover, said material or materials may be used alone or inadmixture with other suitable well-known classes of demulsifying agents.

It is well known that conventional demulsifying agents may be used in awater-soluble form, or in an oil-soluble form, or in a form exhibitingboth 011- and water-solubility. Sometimes they may be used in a formwhich exhibits relatively limited oilesolubility. However, since or 1 to20,000, or 1 to 30,000, or even 1 to40,000, or lto 50,000 as indesalting practice, such an apparent'insolubility in oil and water isnot significant because said reagents undoubtedly have solubility withinsuch concentrations. This same fact is true in regard to the material ormaterials employed as the demulsifying agent of my process.

In practicing the present process the treating or demulsifying agent isemployed in the conventional manner, well known to the art, describedfor example in Patent 2,626,929, dated January 27, 1953,. Part 3 andreference is made thereto for a description of conventional proceduresbfdemulsifying, including batch, continuous and down-the-holedemulsificatiorr, the process.- essentially involving introducing asmall amount of demu1siv fier into a large amount of emulsion withadequate admixture, with or without the application of heat, andallowing the mixture to stratify.

In many instances the oxyalkylated products herein specified asdemulsifiers can be conveniently used without dilution. However, theymay be diluted as desired with any suitable solvent. For instance, bymixing 75 parts by weight of an oxyalkylated derivative, for example,theproduct of Example 12 with 15 parts by weight of xylene and parts byweight of'isopropyl alcohol, an excellent demulsifier is obtained.Selection of the solvent will vary, depending upon the solubilitycharacteristics of the oxyalkylated product, and ofcourse will bedictated in part by economic considerations, i. e., cost.

Thev products herein described may be used not only in diluted form, butalso may be used admixed with some other chemical demulsifier. suchcombination is the following:

Oxyalkylated derivative, for example, the product of Example 1e, 20%;

A cyclohexylamine salt of a polypropylated naphthalene monosulfonicacid, 24%;

An ammonium salt of a polypropylated napthalene. monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleumsu'lfonic acid, 12%; i

A high-boiling aromatic petroleum solvent,

Isopropyl alcohol, 5%.

The above proportions are all weight percents.

A mixture which illustrates Having thus described my invention, what Iclaimas new and desire to secure by Letters Patent, is:

1. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters obtained by the manufacturingprocess of esterifying (A) an oxyalkylated aminemodified phenol-aldehyderesin condensate with (B) a polycarboxy acid; and oxyalkylatedcondensate being obtained by the process of first condensing (a) anoxyallcylation-susceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenolaldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei: per resin mole.- cule; said resin being difunctionalonly: in regard to methylol-forming reactivity; said resinbeingderived'by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol;said resin being formedzin the sub.- stantial absence of trifunctionalphenols; said phenol being of the formula in. which R is an aliphatichydrocarbon radical havingat least 4 and not more than 24 carbon atomsand substi- 32 tuted in the 2,4,6 position; (b) a basic hydroxylatedsecondary monoaminevhaving not more than 32 atoms in any group attachedto the amino nitrogen atom, and ('6) formaldehyde; said condensationreaction being. conev oxide, butylene oxide, glycide and methylglycide;the ratio of polycarboxy acid reactant to oxyalkylated reactant beingone mole of the former for each hydroxyl group present in the latter.

2. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters obtained by the manufacturingprocessof esterifying (A) an oxyalkylated amine-modified phenol-aldehyderesin condensate with (B) a polycarboxy acid; said oxyalkylatedcondensate being obtained by the process of first condensing (a) anoxyalkylationsusceptible, fusible, non-oxygenated organicsolvent-soluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei per resin molecule; said resin being difunctional onlyin regard to methylolforming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absenceof trifunctional phenols; saidphenol being of the formulain which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (0) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the reactants and resultants ofreaction; with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the further proviso that theratio of reactants be approximately 1,2 and 2 respectively; and with thefinal proviso that the resinous condensation productresulting from theprocess be heat-stable and oxyalkylation-susceptibl'e; followed by anoxyalkylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene tained by the process of first condensing (a) anoxyalkylation-susceptible, fusible, non-oxygenated organicsolventsoluble, water-insoluble, low-stage phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6phenolic nuclei resin molecules; said resin being difunctional only inregard to methylol-forming reactivity; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and reactive toward said phenol; said resinbeing formed in the substantial absence of trifunctional phenols; saidphenol being of the formula in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 24 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (c)formaldehyde; said condensation reactionbeing conducted at a temperature sufficiently high to eliminate Waterand below the pyrolytic point of the reactants and resultants ofreaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge con necting the aminonitrogen atom with a resin molecule; with the added proviso that theratio of reactants be approximately 1,2 and. 2, respectively; with thefurther proviso that said procedure involve the use of a solvent; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable and oxyalkylation-susceptible; followedby an oxyalkylation step by means of an alpha-beta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide; the ratio of polycarboxy acid reactant to oxyalkylatedreactant being one mole of theformer for each hydroxyl group present inthe latter.

4. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters obtained by the manufacturingprocess of esterifying (A) an oxyalkylated amine-modifiedphenol-aldehyde resin condensate with (B) a polycarboxy acid; saidoxyalkylated condensate being obtained by the process of firstcondensing (a) an oxyalkylationsusceptible, fusible, non-oxygenatedorganic solventsoluble, water-insoluble, low-stage phenol-formaldehyderesin having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forn1ing reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is analiphatic hydrocarbon radical having at least 4 and not more than 24carbon atoms and substisultants of reaction, with the proviso that thecondensertion reaction be conducted so as to produce a significantportion of the resultant in which each of the three reactants havecontributedpart of the ultimate molecule by virtue of aformaldehyde-derived methylene bridge connecting the amino nitrogen atomwith a resin molecule; with the added proviso that the ratio ofreactants be approximately 1,2 and 2, respectively; with the furtherproviso that said precedure involve the use of a solvent; and with thefinal proviso that the resinous condensation product resulting from theprocess be heat-stable and oxyalkylation-susceptible; followed by anoxyalltylation step by means of an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide; the ratio of polycarboxy acid reactant to oxyalkylatedreactant being one mole of the former for each hydroxyl group present inthe latter.

5. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters obtained by the manufacturingprocess of esterifying (A) an oxyalkylated amine-modifiedphenol-aldehyde resin condensate with (B) a polycarboxy acid; saidoxyalkylated condensate being obtained by the process of firstcondensing (a) an oxyalkylationsusceptible, fusible, non-oxygenatedorganic solventsoluble, water-insoluble, low-stage phenol-formaldehyderesin having an average molecular weight corresponding to at least 3 andnot over 6 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylol-forming reactivity; said resinbeing derived by reaction between a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is analiphatic hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in the 2,4,6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms inany group attached to the amino (c) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminateWater and below the pyrolytic point of the reactants and resultants ofreaction, with the proviso that the condensation reaction be conductedso as to produce a significant portion of the resultant in which each ofthe three reactants have contributed part of the ultimate molecule byvirtue of a formaldehydederived methylene bridge connecting the aminonitrogen atom with a resin molecule; with the added proviso that theratio of reactants be approximately 1,2 and 2, respectively; with thefurther proviso that said procedure involve the use of a solvent; andwith the final proviso that the resinous condensation product resultingfrom the process be heat-stable and oxyalkylation-susceptible; followedby an oxyalkylation step by means of an alphabeta alkylene oxide havingnot more than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide andmethylglycide; the ratio of polycarboxy acid reactant to oxyalkylatedreactant being one mole of the former for each hydroxyl group present inthe latter. 7 I

6. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydropileproducts being acidic fractional esters obtained by the manufacturingprocess of esterifying (A) an oxyalkylated amine-modifiedphenol-aldehyde resin condensate with (B) a polycarboxy acid; saidoxyalkylated condensate being obtained by the process of firstcondensing (a) an oxyalkyla' in which R is an aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms andsubstituted in the 2,4,6 position; (b) a basic hydroxylated secondarymonoamine having not more than 32 carbon atoms in any group attached tothe amino nitrogen atom, and (c) formaldehyde; said condensationreaction being conducted at a temperature sufficiently high to eliminatewater and below the pyrolytic point of the'reacitants and resultants ofreaction, with the proviso that the condens'ation reaction be conductedso as to produce a signifi'cant portion of the resultant in which eachof the three reactants have contributed part of the ultimate molecule byvirtue of a formaldehyde-derived methylene bridge connecting the aminonitrogen atom with a resin inolecule; with the added proviso that theratio of reactants be approximately 1,2 and 2, respectively; with thefurther proviso that said procedure involve the use of .a solvent; andwith the final'proviso that the resinous. condensation product resultingfr'oin the process be beatst'able and oxyalkylation-susceptible;followed by an oxyalkylation step by means of an alpha-beta alkyleneoxide having not more than 4 carbon atoms and selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycideand methylglycide; the radio of polycarboxy acid reactant tooxyalkylatedreactant.be ing'one mole of the former'for each'hydroxyl group presentin the latter. I

7. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters obtained by the manufacturingprocess of esterifying (A) an oxyalkylate'd amine-modifiedphenol-aldehyde resin condensate with (B) a polycarboxy acid;said'oxyalkylated condensate being obtained by the process of firstcondensing (a) an oxyalkylation-susceptible, fusible, non-oxygenatedorganic solvent-soluble, water-insoluble, low-stage phenol-formaldehyderesin having an average molecular weight'correspondi'ng to 'at'least 3and not over 5 phenolic'nuclei per resin'molecule; said resin beingdifunctional only in regard to 'methylol-forming reactivity; said resinbeing'derived by reaction be tween a difunctional monohydric phenol andformaldehyde; said resin being formed in the substantial absence oftrifunctional phenols; said phenol being of the formula in which R is analiphatic hydrocarbon radical having at least 4 and not more than 14carbon atoms and substituted in.the 2,4,6 position; (b) a basichydroxylated secondary monoamine having not more than 32 carbon atoms inany group attached to the amino nitrogen atom, and (0) formaldehyde;said condensation reaction being conducted at a temperature above theboiling point of water and below 150 C., with the proviso that thecondensation reaction be conducted so asto produce a significant portionof the resultant in which each of the three reactants have contributed.part of the ultimate molecule by virtue of a formaldehyde-derivedmethylene bridge connecting the amino nitrogen atom with 'a resinmolecule; with the added proviso that the ratio of reactants beapproximately 1,2 and 2; respectively; with the further proviso thatsaidprocedure involve the use of a solvent; and with the final provisothat the resinous condensation product resulting from the process beheat-stable and oxyalkylation-susceptible; followed by an oxyalkylationstep by means of an alpha-beta alkylene oxide having not more. than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butyl ene oxide, glycide and methylglycide; the ratioof polycarboxy acid'reactant to oxyalkylated reactant being one mole ofthe former for each hydroxyl group present in the latter.

8. A process for breaking petroleum emulsions of the water-in-oil typecharacterized by subjecting the emulsion to the action of a demulsifierincluding synthetic hydrophile products; said synthetic hydrophileproducts being acidic fractional esters'obtained by the manufacturingprocess of esterifying (A) an oxyalkylated amine-modifiedphenol-aldehyde resin condensate with (B) a polycarboxy acid; saidoxyalkylated condensate being obtained by the process of firstcondensing (a) an oxyalkylation-susceptible, fusible, non-oxygenatedorganic solvent-soluble, water-insoluble, low-stage phenol-formaldehyderesin having an average molecular weight corresponding to at least 3 andnot over 5 phenolic nuclei per resin molecule; said resin beingdifunctional only in regard to methylolforming reactivity; said resinbeing derived by reaction of trifunctional phenols; said phenol being ofthe formula in which R is a para-substituted aliphatic hydrocarbonradical having at least 4 and not more than 14 carbon atoms; ([1) abasic hydroxylatcd secondary monoamine having not more than 32 carbonatoms in any group attached to the amino nitrogen atom, and (c)formaldehyde; said condensation reaction being conducted at atemperature aboveithe boiling point of water and below C., with theproviso that the condensation reaction be conducted so as to'produce asignificant portion of the resultant in which each of the threereactants have contributedpar't of the ultimate'molecule by virtue of aformaldehyde-derived :methylene' bridge connecting the amino nitrogenatom with a resin molecule; with the added proviso that the ratio'ofreactants be approximately 1,2 and 2, respectively; with'the furtherproviso that said procedure involve'the use of a solvent; and'with thefinal proviso that the resinous condensation product resulting from the'proceess be heat-stable and oxyalkylation-susceptible;;followed by anoxyalkylation step by means of an alpha-beta :alkylcne oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene bxide, bntylene oxide, glycidc andmethylglycide; the ratio of polycarboxy acid reactant to oxyalkylatedreactant being one mole of the former for each hydroxyl group presentin'the latter.

9. The process .of claim 1 wherein the oxyalklation step'is limited tothe use of 'both"ethylcneoxi'de and propylene oxide in combination, andthe csterification step is limited to the use of a dicarboxy acid'havingnot over 8 carbon'at'oms.

10. The process of claim-'2 whereinthe-oxyalkylation step is limited tothe 'useof both ethylene oxide and propylene oxide in combination, andtheesterification over 8 carbon atoms.

37 '11. The process of .claim 3 wherein the oxyalkylation step islimited to the use of both ethylene oxide and propylene oxide incombination, and the esterification step is limited to the use of adicarboxy acid having not over 8 carbon atoms.

12. The process of claim 4 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over 8 carbon atoms.

13. The process of claim 5 wherein the oxyalkylation 'step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over 8 carbon atoms.

14. The process of claim 6 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over 8 carbon atoms.

15. The proceess of claim 7 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over 8 carbon atoms.

16. The process of claim 8 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over 8 carbon atoms.

17. The process of claim 1 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufficientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

18. The process of claim 2 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are suflicientto produce an emulsion when said xylene solution is shaken vigorouslywith l to 3 volumes of water.

19. The process of claim 3 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufficientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of Water.

20. The process of claim 4 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufiicientto produce an emulsion when said xylene solution is shaken vigorouslywith l to 3 volumes of water.

21. The process of claim 5 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are suflicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

V 22. The process of claim 6 with'the proviso that-the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal Weight of xylene are sufiicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

23. The process of claim 7 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal Weight of xylene are sufiicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

24. The process of claim 8 with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification em ployed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufiicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

25. The process of claim 1 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over eight carbon atoms; and with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sulficientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

26. The process of claim 2 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over eight carbon atoms; and with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are suflicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

27. The process of claim 3 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over eight carbon atoms; and with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufiicientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

28. The process of claim 4 wherein the oxyalkylation step is limited tothe useof both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to the use of a dicarboxy acid havingnot over eight carbon atoms; and with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of a member of the classconsisting of (a) the anhydro base as is, (b) the free base, and (c) V39 the salt tof hydroxy acetic acid,-in an equal weight of xylene ares'uflicient to produce ,an emulsion when said xylene solution'isshaken-vigorouslywith 1 to 3 volumes of water. s

29. The process of claim 5. wherein the oxyalkylation stcp'i's limitedto the use of both ethylene oxide and propylene oxide in combination,and'the esterification step is limited to theme of a dicarboxy acidhaving not over eight carbon atoms; and with the proviso that thehydrophileproperties of the product obtained by oxyalkylation of thecondensate prior to esterification employed'in'the form of a member ofthe class consisting. of (a) the'anhydro base 'as is, (b) the free base,and (c) the salt of hydroxy acetic acid, in an equal weight of xyleneare suflicient to produce an emulsion when said xylene solution isshaken vigorously with 1 to 3 volumes of water. t

30. The process of claim 6 wherein the oxyalkylation step is limited ,tothe use of both ethylene oxide and propylene oxide in combination, andthe esterification step is limited to theme of -a dicarboxy acid havingnot over eight carbon atoms; and with the proviso that the hydrophileproperties of the product obtained by oxyalkylation of the condensateprior to esterification employed in the form of amember of the classconsisting of (a) the anhydro'base as is, (b) the free base, and (c) thesalt of hydroxy acetic acid, in an equal weight of xylene are sufficientto produce an emulsion when said xylene solution is shaken vigorouslywith 1 to 3 volumes of water.

31. The process of claim 7 wherein the oxyalkylation step is limited tothe use of both ethylene oxide and propylene oxide "in combination, and:the .esterific'ation step i's'limited to the use of aidicarboxy acidhaving not over eight carbon atomsyand'with the proviso that thehydrophilc properties of the product obtained by oxyalkylation of thecondensate prior to esterification employed in the form of a member ofthe class consisting of (a) the anhydro base as is, (b) the free base,and (c) the salt of hydroxy acetic acid, vin an equal weight of xyleneare sufiicient to produce an emulsion when said xylene solution isshaken vigorously with 1 to 3 volumes of Water.

32. The process of claim 8 wherein the oxyalkylation step is limited tothe usefof both ethylene oxide and propylene oxide in combination, andthe esterification,

step is limited to the use of a dicarboxy acid having not over eightcarbon atoms; and with the proviso that the hydrophile properties of theproduct obtained by oxyalkylation of the condensate prior toesttarificationemployed in the form of a member-of the class consistingof (a) the anhydro base as is, (b) the free base, and (c) the salt ofhydroxy acetic acid, in an equal weight of xylene are sufficient toproduce an emulsion when said xylene solution is shaken vigorously with1 to 3 volumes of water.

References Cited in the file of this patent UNITED "STATES PATENTS2,031,557 Bru'son Feb. 18, 1936 2,454,544 Bock et a1 Nov. 23, 19482,542,012 De Groote et al. Feb. 20, 1951

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPECHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIERINCLUDING SYNTHETIC HYDROPHILE PRODUCTS; SAID SYNTHETIC HYDROPHILEPRODUCTS BEING ACIDIC FRACTIONAL ESTERS OBTAINED BY THE MANUFACTURINGPROCESS OF ESTERIFYING (A) AN OXYALKYLATED AMINEMODIFIED PHENOL-ALDEHYDERESIN CONDENSATE WITH (B) A POLYCARBOXY ACID; AND OXYALKYLATEDCONDENSATE BEING OBTAINED BY THE PROCESS OF FIRST CONDENSING (A) ANOXYALKYLATION-SUSCEPTIBLE, FUSIBLE NON-OXYGENATED ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOLALDEHYDE RESIN HAVINGAN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLYIN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESINBEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAIDPHENOL BEING OF THE FORMULA